Low interfacial tension surfactants for petroleum applications

ABSTRACT

The invention relates to a class of novel surfactants that have utility in the recovery and/or extraction of oil.

RELATED APPLICATION

This application is a continuation-in-part of application Ser. No.12/481,072 filed on Jun. 9, 2009, which claims the benefit of U.S.Provisional Application No. 61/060,004 filed on Jun. 9, 2008. The entireteachings of the above applications are incorporated by referenceherein.

FIELD OF THE APPLICATION

The application relates generally to surfactants useful for petroleumapplications.

BACKGROUND

A number of problems in the petroleum industry derive from theviscosity, surface tension, hydrophobicity and density of crude oil.Heavy crude oil in particular, having an API gravity of less than 20degrees, is difficult to transport due to its viscosity, and isdifficult to remove from surfaces to which it has adsorbed, due to itshydrophobicity and immiscibility with water. Extra-heavy crude oil orbitumen, having an API gravity of less than 10 degrees, is heavier thanwater, so that it can sink to the bottom of a water formation, causingsub-surface contamination.

The properties of crude oil contribute to the limitations of oilrecovery from traditional oil fields. Conservative estimates suggestthat 30% of the technically recoverable oil in U.S. oil fields isinaccessible due to the adsorption of the residual oil to porousgeologies. Technologies to unlock the oil in these so-called “dead”wells presently involve the use of hot water injections with expensivesurfactants, chemistries that are applied to overcome the hydrophobicityof the adsorbed oil so that it can be mobilized.

The properties of crude oil also contribute to the difficulty ofenvironmental remediation following, for example, an oil spill onto abody of water. The high interfacial tension causes the oil to float onthe water and adhere to plants, animals and soil. As the aromaticconstituents of the oil evaporate, the heavier residues can sink,contaminating the subsurface structures. Current treatment of spilledoil on water surfaces relies on time-consuming and expensive biologicaldegradation of the oil. Thick, adherent crude oil cause environmentalproblems in the oil fields as well. Oil deposits attached to vehiclesand equipment must be cleansed with jets of hot water and caustics.

The viscosity of heavy crude oil makes the substance difficult andexpensive to transport to upgrading facilities. Because of itsviscosity, a significant amount of energy is required to pump it throughpipelines to a refinery. Furthermore, the viscosity affects the speed atwhich the heavy crude oil can be pumped, decreasing the overallproductivity of an oil field. Exploiting certain oil fields or other oildeposits may be economically unfeasible to develop at present because ofthe transportation-related costs.

Surfactants have been widely used in the petroleum industry toameliorate the effects of crude oil's physical properties. Surfactantmolecules consist of hydrophobic and hydrophilic parts. Theiramphiphilic nature allows them to be adsorbed at an oil/water interface,forming micelles that allow the interfacial tension between oil andwater to be reduced.

Surfactants are sometimes used for desalting of crude oil. Desaltingrefers to the process of removing salts from oil, making the oil moresuitable for further refining. The salts are typically dissolved inwater that is associated with oil, so the removal of water has multiplebenefits. The presence of water reduces the energy content of oil, andit carries salts that can harm catalyst performance or cause corrosion.Ethoxylated nonylphenols have been used for desalting of crude oil, butthese compounds pose hazards to the environment.

Furthermore, surfactant technologies for the aforesaid petroleumapplications typically are expensive or must be used at highconcentrations. Additionally, demulsification can prove to be difficult,as these surfactants are designed for emulsifying purposes.Demulsification typically requires added materials and steps to break upthe emulsion, which increases the effective cost of use. Furthermore,the salts present in nature can inactivate many surfactant technologies.In addition, other surfactant technologies for petroleum applicationsare tailored only to oils of a limited composition.

The development of a technology that can provide emulsion and favorabletransport properties while maintaining the ability to demulsify ondemand, all under variable conditions of salinity, remains unmet in theart. Such a technology would have wide reaching impact across theoilfield chemical sector in applications such as those mentioned above,particularly if the material could be inexpensively produced and couldbe applied to a variety of oil types.

SUMMARY

The invention relates to the discovery that novel surfactants andsurfactant compositions have good to excellent properties in recoveringor extracting oil, such as fossil fuels.

Accordingly, in some embodiments, the invention relates to a compoundhaving the formula I:

wherein Ar is a substituted or unsubstituted aryl, aralkyl (e.g.,benzyl) or heteroaryl group; in some embodiments, Ar is a substituted orunsubstituted aryl or heteroaryl group; preferably a substituted orunsubstituted phenyl group;p is 1 or 2; preferably 2;m and n are independently 0, 1, 2, 3, 4, or 5; preferably 1;each of G₁ and G₂ are independently absent, O, S, NR₂, C(O)O, OC(O), CO,CONR₂, or NR₂CO; preferably each G₁ and G₂ are independently O or C(O)O;each R₂ is independently H or a lower alkyl; in some embodiments, thelower alkyl is a C1 to C5 alkyl;each G₃ is independently absent, (CH₂)_(q) or G₁;q is 1, 2, 3, 4 or 5;R is a hydrophilic group; preferably the hydrophilic group is COOH, or ahydrophilic polymer; such as a polyethylene glycol or apolypropyleneoxide;R₁ is a saturated or unsaturated hydrophobic aliphatic group; in someembodiments, R₁ is C₅ to C₁₈ alkyl, alkenyl or alkadienyl, preferably astraight chain C₅ to C₁₈ alkyl;wherein, when p is 1, Ar is substituted by one or more of OR₂, SR₂ andN(R₂)₂;preferably, when p is 1 Ar is substituted by OH, SH or NH₂.

In one preferred embodiment, G₁ is C(O)O, G₂ is absent and n is 0.Alternatively, where G₁ is O, G₂ is not absent, and is preferably O orC(O)O.

A particularly preferred surfactant is a compound having the formula II:

wherein R₅ is a hydrophilic group; andR₄ is a saturated or unsaturated hydrophobic aliphatic group.

The invention further relates to a compound having formula III:

wherein G₁ is selected from the group consisting of S, NR₂, C(O)O,OC(O), CO, CONR₂, and NR₂CO; preferably G1 is C(O)O;each R₂ is independently H or a lower alkyl;wherein, R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ are each independently, H, OH,halogen, C₁-C₅ alkyl, C₁-C₅ alkoxy, a C₃-C₇-cycloalkyl group, a phenylgroup optionally substituted by hydroxyl, halogen, lower alkyl or loweralkoxy, or Fragment I having the formula shown below:

wherein R₁, m and G₁ are as defined above;wherein at least one of R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ is Fragment I or OH;or a salt thereof.

A particularly preferred surfactant is a compound having the formula IV:

wherein m and R₁ are as defined above.

Preferred compounds of formula IV are compounds wherein m is 1 and R₁ isa straight chain C₅ to C₁₈ alkyl.

In other aspects, the invention relates to a composition comprising anaromatic compound and a substituted succinic anhydride, wherein

the aromatic compound has the Formula VIII:

Ar-[G₄]_(p); and

the substituted succinic anhydride has the Formula IX:

wherein Ar is selected from the group consisting of aryl, arylalkyl andheteroaryl, each optionally substituted;each G₄ is independently selected from the group consisting of OR₂, SR₂,N(R₂)₂, COOR₂, OCOR₂, COR₂, CON(R₂)₂ and N(R₂)₂CO;each R₂ is independently selected from the group consisting of H andlower alkyl;R₈ is a saturated or unsaturated hydrophobic aliphatic group; andp is 1 or 2. In some embodiments, each R₂ is independently selected fromthe group consisting of H and C1-C6 alkyl. In some embodiments, each G₄is independently selected from OR₂ or NR₂. In additional embodiments,the invention is directed to a method preparing a surfactant compositioncomprising mixing a compound of Formula VIII with a compound of FormulaIX.

In additional embodiments, the invention is directed to a compositioncomprising an aromatic compound and a substituted succinic anhydride,wherein

the aromatic compound is resorcinol; and

the substituted succinic anhydride has the Formula IX:

wherein R₈ is a saturated or unsaturated hydrophobic aliphatic group. Incertain aspects, the resorcinol is m-resorcinol.

In an additional embodiment, the invention is directed to a compositioncomprising an aromatic compound and a compound of Formula X wherein

the aromatic compound has the formula VIII:

Ar-[G₄]_(p); and

the compound of Formula X is:

wherein Ar is selected from the group consisting of aryl, arylalkyl orheteroaryl; preferably phenyl or benzyl;each G₄ is independently selected from the group consisting of OR₂, SR₂,N(R₂)₂, COOR₂, OCOR₂, COR₂, CON(R₂)₂ and N(R₂)₂CO; preferably, OR₂ orN(R₂)₂;each R₂ is independently selected from the group consisting of H andlower alkyl;R₈ is a saturated or unsaturated hydrophobic aliphatic group; andp is 1 or 2. In some embodiments, the composition comprising Formula Xand an aromatic compound further comprises an alkylene oxide, suchethylene oxide or propylene oxide.

In yet another embodiment, the invention is a compound having theFormula (XI):

wherein Ar₂ is a substituted or unsubstituted phenyl or benzyl;p is 1 or 2;m is 1 or 2;n is 0 or 1;each G₁ is independently selected from the group consisting of OC(O),C(O)O, C(O), C(O)NR₂ and NR₂CO;each G₂ is absent;each R₂ is independently H or a lower alkyl;each G₃ is independently absent, or (CH₂)_(q);q is 1, 2, 3, 4 or 5;R is a hydrophilic group; andR₁ is a saturated or unsaturated hydrophobic aliphatic group.

In some aspects, the invention is directed to a compound having theFormula XII:

wherein t is 0 or 1;

G₅ is O or NH;

and R is as defined above.

In other embodiments, the invention is directed to a compound having theFormula (XIII):

wherein t is 0 or 1 and R is as defined above.

In an additional embodiment, the invention relates to a compound havingthe Formula XIV:

L-G₅-Ar-G₅-M;

wherein Ar is aryl, arylalkyl and heteroaryl, each optionallysubstituted; preferably, Ar is phenyl;each G₅ is independently O or NH;L is a hydrophilic polyethylene glycol glycidyl ether; andM is a hydrophobic glycidylalkyl ether.

The invention further relates to a method for extracting oil from ancomprising:

(a) adding a compound or composition of the invention to an oil mixture,and

(b) collecting the oil.

An oil mixture is a mixture comprising oil and at least one othercomponent. The oil mixture can comprise oil sands, waterborne oil slicksor oil deposits. Further, the methods of the invention can comprise theadditional steps of adding water or transporting the mixture via apipeline. In another embodiment, the compounds and compositions of theinvention can be used in methods of degreasing machinery, such as thoseused in oil or bitumen production.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates examples of critical micelle concentration ofcompositions (a 1:1 composition of m-resorcinol and alkylated succinicanhydride (Eka SA 210 brand alkylated succinic anhydride) and a 1:2composition of m-resorcinol and alkylated succinic anhydride of formulasshown below; labeled R1 and R2, respectively).

FIG. 2 shows a plot of CMC as a function of pH for two compositions, a1:1 composition of m-resorcinol and alkylated succinic anhydride (Eka SA210 brand alkylated succinic anhydride) and a 1:2 composition ofm-resorcinol and alkylated succinic anhydride (described in more detailin the Examples).

FIG. 3 compares the capabilities of the surfactant compositions (1:1composition of m-resorcinol and alkylated succinic anhydride (Eka SA 210brand alkylated succinic anhydride) and a 1:2 composition ofm-resorcinol and alkylated succinic anhydride) in emulsifying andtransporting heavy crude oils, measuring the viscosity of dilutedbitumen.

FIG. 4 shows a magnified image of oil droplets.

FIG. 5 is a graph showing emulsion viscosity as a function of percentage(%) surfactant solution content.

DETAILED DESCRIPTION General Formulations

Disclosed herein are compositions, systems and methods related toultra-low interfacial tension (“IFT”) surfactants for applications inthe petroleum industry. In certain embodiments, the present disclosureis based on the discovery that certain ester surfactants andcompositions comprising resorcinol and alkenylated succinic anhydrideare highly effective surfactants for petroleum applications, and can beused as additives in petroleum processing, oil sands extraction andprocessing, environmental remediation, enhanced oil recovery, and thelike.

In one embodiment, compositions of particular use in these systems andmethods can include at least one compound of the formula (V):

wherein R₁ is a hydrophobic group as defined above.

In alternate embodiments, compositions of particular use in thesesystems and methods can include at least one compound of formula (VI):

wherein R₆ and R₇ are each independently a hydrophobic group.

In one embodiment, compositions of particular use in these systems andmethods can include at least one compound of the formula (VII):

wherein R₁ is as defined above for Formula I.

In yet another embodiment, the surfactant compound has the Formula XI,XII or XIII as shown above.

The invention also encompasses compositions comprising an aromaticcompound having the Formula VIII and a substituted succinic anhydridehaving the Formula IX. In an additional embodiment, the invention isdirected to compositions comprising an aromatic compound having theFormula VIII and an ether compound having the Formula X. The succinicanhydride of Formula IX and the compound of Formula X are substitutedwith a hydrophobic aliphatic group. In some aspects, the hydrophobicaliphatic group is selected from the group consisting of alkyl, alkenyl,alkadienyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heteroaryl. Incertain embodiments, the aromatic compound comprises an optionallysubstituted benzyl or optionally substituted phenyl core. In additionalaspects of the invention, G₄ is selected from the group consisting ofOR₂ or N(R₂)₂. In yet another embodiment, the invention is a compositioncomprising resorcinol (for example, m-resorcinol) and a succinicanhydride having the Formula IX.

The compounds and compositions described herein can be used assurfactants. The inventive surfactant compounds comprise an aromaticcore with pendant aliphatic hydrophobic and hydrophilic portions. Theinventive compositions comprise an (i) aromatic compound and (ii) asubstituted succinic anhydride or a substituted ether which each aresubstituted with hydrophobic groups. As will be understood by one ofskill in the art the hydrophobic portion of the surfactant compound orcomposition can comprise one or more hydrophobic groups or substituents.Similarly, the hydrophilic portion of the inventive compounds cancomprise one or more hydrophilic groups or substituents. Attachedaliphatic hydrophobic portions or groups can consist of linear orbranched, saturated or unsaturated, substituted or unsubstituted higheralkyls. For example, the hydrophobic group can be derived from alkaneswith or without internal or terminal alkenes. In some embodiments, thehigher alkyl comprises at least five carbon atoms. In other embodiments,the higher alkyl is a C₅ to C₁₈ alkyl, alkenyl or alkadienyl, or C5 toC20 alkyl, alkenyl or alkadienyl, or C8 to C20 alkyl, alkenyl oralkadienyl. Hydrophilic portions or groups can be an ionizable groups,including, for example, amines and carboxylic acids. Hydrophilic groupsalso include hydrophilic polymers, including, but not limited to,polyalkylamine, poly(ethylene glycol), poly(propylene glycol) orpolyethylene glycol/polypropylene glycol copolymers. Nonionichydrophilic materials such as polyalkylamine, poly(ethylene glycol) orpoly(propylene glycol) can be used to increase hydrophilicity or aidstability in salt solutions.

In some embodiments, the aliphatic groups include saturated orunsaturated carbon chains, preferably between five and twenty units inlength, or five and eighteen units in length, or eight and twenty unitsin length, or hydrogen. The carbon chains can optionally be unsaturatedand, when present, reside anywhere along the carbon chain.

The aromatic core of the inventive compounds or the compounds in thecompositions (e.g., Ar or Ar₂ as described above) can be carbocyclic orheterocyclic, monocyclic or polycyclic, substituted or unsubtstituted.Preferred aryl groups can be derived from resorcinol, phenol, phenylamine, creosol, benzyl alcohol, benzyl amine, naphthalene, anthracene,pyrene, tetrahydronaphthyl, indanyl, idenyl and the like. Heteroaromaticstructures such as thiophene, selenophene, silole, pyrrole, pyridine,furan, imidazole, indole, pyrazinyl, pyrimidinyl, pyrazolyl, imidazolyl,thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, furanyl,quinolinyl, isoquinolinyl, benzimidazolyl, benzooxazolyl, quinoxalinyl,and the like can also be used as the aromatic core. The term“substituted” refers to substitution by independent replacement of oneor more of the hydrogen atoms thereon with substituents including, butnot limited to, —OH, —NH₂, —NH—C₁-C₁₂-alkyl, —O—C₁-C₁₂-alkyl, —SH, and—S—C₁-C₁₂-alkyl, C1-C12 alkyl, and C1-C12 alkenyl.

In certain aspects of the invention, the hydrophilic portion ofcompounds of the invention (e.g., R as described above) is one or moreionizable carboxylic acid groups, which groups, in some embodiments, canmake up the totality of the hydrophilic portion. By themselves, thecarboxylic acid portions are not enough to effectively stabilizeemulsions formed by the mixture of a waterborne suspension of thedisclosed surfactant compounds. Addition of a small amount of base(greater than about pH 8 or between a pH of about 8 and about 9) issufficient to ionize, leaving a more active, emulsion-forming material.The emulsion can later be destabilized by adding acid to the material,removing the charge stabilization and splitting the two incompatiblephases.

Changing pH is one method of enabling and disabling the surfactantbehavior; however, compounds of formula (I) and formula (III) aretypically unstable hydrolytically.

In other aspects of the invention, the hydrophilic portion of compoundsof the invention is one or more polymers or copolymers containing ethergroups. These polymers will impart the compounds with a cloud point. Thecompounds will display solubility in water at temperatures below thecloud point and, as a consequence, will be able to emulsify oil.However, upon increasing the temperature over the cloud point, thecompounds will become less soluble in water and will lose theiremulsification properties. This behavior is reversible because nofunctional groups are cleaved in the process. An example of compoundsexhibiting this behavior are compounds having the Formula (XIII).

Some examples of compounds of Formula XIII can be obtained by reacting:

Aromatic (primary or secondary) amines with polyetherglycidyl ethers.Examples of amines are: ortho, meta or para phenylene diamine. Thepolyether can be polyethyleneglycol diglycidyl ether. Another example ofthese compounds can be obtained by reacting an aromatic diamine with ahydrophilic polyethylene glycol glycidyl ether and a hydrophobicglycidyl alkyl ether. The resulting product has comprises a rigidaromatic unit in the middle and 2 linear groups hanging from it, one ofthe groups being hydrophilic and the other hydrophobic.

The tunable behavior of the inventive surfactants and surfactantcompositions has utility for petroleum-related applications. Forexample, if the residence time of the oil in a pipeline is known or canbe estimated, the amount of base can be calculated and added with thesurfactant to cause decomposition begin in the pipeline and separationto occur immediately after the emulsion reaches its destination. Thishas the benefit of decreasing residence time in a storage facility whilethe emulsion breaks.

Applications

Environmental Remediation

By taking advantage of the low IFT behavior of the surfactant compoundsand compositions disclosed herein, such surfactant compounds andcompositions can be suitable for applications where undesired petroleumproducts pose an environmental problem. Oil cleanup using surfactantcompounds and compositions may be required for two different types ofcontamination. First, as an oil slick dispersant, the surfactantcompounds and compositions described herein can be used on waterborneslicks, acting as a dispersing agent. The surfactant compounds andcompositions will act to disperse the oil into the water body itself andencourage biodegradation through natural decomposition means.Additionally, a solution of surfactant or surfactant composition can beused to remove physiosorbed crude or refined oils from inorganic rocks,sand, or other substrates as an emulsion.

Oil Sands Extraction

Oil sands comprise heavy petroleum products coating sand and clay, anassemblage that is similar to certain artificial composites that areformed during a man-made oil spill, as described above. The systems andmethods described herein can be useful for extracting bitumen from theother components of the tar sands material. Currently, mined oil sandsare extracted using hot water, a process that causes the less densebitumen to flow off the sand and float to the surface of a settlingtank. This so-called “primary froth” is contaminated with variousmaterials derived from the mined products (solid particles, clay, andsand). Current froth treatment utilizes naphtha, a valuable fraction ofpurified petroleum, to dilute the bitumen and decrease the viscosity tothe point of flowability. This allows solids and water to be removed bysettling and centrifugation methods. By using an aqueous solution ofsurfactant or the compositions described herein as the dilution mediuminstead of naphtha, the latter solvent can be replaced with water andsurfactant, thus decreasing the cost of purifying the froth.Additionally, when the surfactant-diluted bitumen is recovered from thewater, the hydrophilic portions associated with the froth (clay, water,salts) preferentially partition to the water phase and be separable fromthe bitumen.

Use of surfactants and surfactant compositions in accordance with thesesystems and methods can further be applied to other aspects of theextraction process, for example in the oil sands strip mining or in-situoperations, where the ability to emulsify the petroleum component of theoil sands ore may enhance the efficiency or economy of separating thebitumen from the insoluble byproducts.

Oil Field Transport Emulsions

Transporting petroleum precursors for further processing is a necessary,though expensive, part of obtaining usable crude oil. When petroleum isobtained as a heavy crude, it needs to be transported to an upgradingfacility for conversion to useful petroleum products. Typically,pipeline transport is the most economical means to accomplish this. Whenoil sands are used as precursors in the production of synthetic crudeoil, they are transported for further processing after extraction andfroth treatment through pipelines as a naphtha-diluted bitumen so thatthey can undergo further upgrading processes, including cracking andcoking, amongst other standard refining operations. For these types ofapplications in the petroleum and tar sands industries, the heavy oil oroil precursor materials (respectively) may be transported throughpipelines as oil-in-water mixtures or emulsions. It is understood thatmore viscous matter being sent through pipelines has a greaterresistance to flow and consequently requires more energy to move anequivalent distance. Hence, decreasing the viscosity of the flowablematter decreases the amount of pumping energy required, and potentiallyimproves the transit time and the productivity of the overall process.Mixing water with crude oil or bitumen can decrease the viscosity ofthese latter substances towards the viscosity of water, but only if awater-continuous emulsion is created. The described low IFT surfactantsand surfactant compositions can compatibilize oil and water into anemulsion that can be pumped with greatly decreased energy requirementsand/or increase the throughput of crude oil or oil precursors to theirdestinations.

Auxiliary Petroleum Applications

There also exist many other opportunities in the oilfield chemicalsector for degreasing applications, as can be accomplished with thesystems and methods disclosed herein. Periodically, machinery used inoil and bitumen production must be cleaned for maintenance andperformance reasons. With petroleum production heading towards heaviercrude reserves, the need for an effective degreaser becomes even moreacute: exposure to heavier crude oils results in thicker, more adherentoil residues that must be removed during the cleaning/degreasingprocesses. The described low IFT surfactants can be an active ingredientin an industrial degreasing formulation for these purposes.

Enhanced Oil Recovery (EOR)

Tertiary oil recovery, also known as “enhanced” or “improved” oilrecovery, makes use of low IFT surfactant and surfactant compositions toproduce oil from wells that have stopped producing of their own accord.Injection of a low IFT surfactant into one of these less productivewells can stimulate production from the residual oil left adhered to thesurface of porous rocks. The compounds and compositions described hereinare useful as low IFT surfactants for EOR. Due to the temperatures andresidence time underground, certain esters made in accordance with theinvention may be too unstable for these applications. In addition, theresident acid groups on the compound of formula (II) are highlysensitive to saline commonly found in well formations.

The compound of formula (II) may be particularly suitable for EORapplications:

R₄ and R₅ are as defined above.

In some embodiments, R₄ can include a linear or branched carbon chainconsisting of five to eighteen carbon atoms. Advantageously, substituentR₄ can be a saturated or unsaturated carbon chain consisting of five toeighteen carbon atoms.

In some embodiments, R₅ can include water soluble oligomers such aspoly(ethylene glycol) or poly(propylene oxide). By using a smallpoly(ethylene glycol) as the hydrophilic portion the substituent R₅, andall ether connectivity, the molecule of formula (II) may desirablywithstand the temperature and salinities found underground for therequisite time period.

In some aspects, the compositions comprising an aromatic compound ofFormula VIII and succinic anhydride having the Formula IX (such as,resorcinol and succinic anhydride having the Formula IX) can be used inEOR applications as described herein.

EOR techniques in accordance with these systems and methods can improvethe mobility of oil while making the rock reservoir water-wet to improveits permeability and allow for the recovery of oil at an increased rate.EOR systems and methods can involve using thickening polymers that canself-assemble at the oil surface and act as an efficient emulsifier. Inembodiments, aqueous fluids can be designed that will increase sweepefficiency and percent recovery for EOR.

It is understood that the efficiency of a displacing fluid can bedefined by the mobility ratio as well as the capillary number. Themobility ratio is indicated by Equation 1.

$\begin{matrix}{M = \frac{k/{\mu ({displacingfluid})}}{k/{\mu ({displacedfluid})}}} & {{Equation}\mspace{14mu} 1}\end{matrix}$

In Equation 1, k is the permeability of the media and μ is the viscosityof the fluid. The mobility ratio indicates the sweeping efficiency of adisplacing fluid. A mobility ratio <1 can mobilize oil while >1 cannot.The capillary number is indicated by Equation 2.

$\begin{matrix}{{Ca} = {V\frac{\mu}{\gamma}}} & {{Equation}\mspace{14mu} 2}\end{matrix}$

In Equation 2, V is the characteristic velocity, μ is the viscosity ofthe displacing fluid and γ is the IFT. The capillary number is adimensionless number that characterizes the relationship of viscosityand IFT of two immiscible fluids. Low capillary number indicatescapillary forces will determine the flow through the rock reservoir. Thepercent oil recovery increases as a function of the capillary number ofa displacing fluid. Fluids such as water that have a high mobility ratioand low capillary number will take the least tortuous path through theformation and therefore are poor displacing fluids.

It is to be understood that a surfactant can give a low mobility ratiowith a high capillary number as a single component system even in lowconcentrations. Although in theory, either a low mobility ratio or highcapillary number can give 100% oil recovery, this is not true inpractice. In embodiments, these systems and methods can provide for acost effective and efficient method for EOR that improves both themobility ratio and capillary number of the displacing fluid. Inembodiments, an amphiphilic polymer can be used to act as a thickener inthe displacing aqueous phase which can self-assemble onto the surface ofoil and act as a surfactant in the oil phase.

EOR processes must be robust enough to survive the subterraneanenvironments that typically see temperatures in excess of 100° C. whilesalinity and dissolved solids can vary greatly. In embodiments, polymersare selected that can withstand high temperatures without degrading. Forexample, hydrophilic groups can shield the polymer from changes in waterchemistry including multivalent cations. Or, for example, the polymercan be diluted and delivered in a brine solution which can significantlyreduce cost. In embodiments, the self-stabilizing polymeric surfactantcan serve to hinder precipitation unless in the presence of a stronghydrophobe. In embodiments, for example, the stability of the polymersurfactant is only broken down in the presence of hydrophobic compoundssuch as oil. At this point, a selected polymer would cease to behave asa polymer slug and would become more like a surfactant. It is understoodthat the presence of a hydrophobe would destabilize the selectedpolymer, and it could undergo a conformation change to a more stablestructure that could effectively emulsify oil. A hydrophobic componentof the selected polymer could penetrate the oil-water interface andeffectively reduce the IFT. The polymer could also have the effect ofslightly reducing the viscosity of the oil in the surrounding area.

In embodiments, these systems and methods can include stimuli-responsivesurfactants templates produced in polymeric form for EOR applications.In embodiments, a polymer could emulsify or demulsify due to a certainstimulus such as pH or temperature. Demulsification, for example, couldbe used to improve oil reclamation in an ex-situ process.

In embodiments, polymeric agents such as polyimide-amine salts ofstyrene-maleic anhydride (SMA) copolymers could be used as surfactantsin accordance with this disclosure. In one embodiment, a SMA copolymerhaving pendant tertiary amine groups containing a salt-forming tertiarynitrogen atom neutralized to the extent of at least about 75 percentwith mono-carboxylic acids, having for example an aliphatic chain of atleast about 8 carbon atoms, could be used. In embodiments, thepolyimide-amine salts useful for EOR can also contain mixed imides,resulting, for example from the reaction of dialkylaminoalkylamines andmonoalkyl amines, or mixed imide-amides resulting from the reaction ofdialkylaminoalkylamines and dialkylamines. In embodiments, salts can beprepared by converting the anhydride rings of styrene-maleic anhydridecopolymers to polyimides containing pendant tertiary amine groups. Thesependant tertiary amine groups can be neutralized with monocarboxylicacids to form salts that have useful properties for EOR. Mixed imideforms of these salts can be obtained by reacting primary alkylamineswith a minor portion of the anhydride groups of the styrene-maleicanhydride copolymer. Similarly, mixed imide-amide forms of the salts canbe obtained by reacting a minor portion of the copolymer anhydridegroups with secondary dialkylamines.

In embodiments, useful polymers in accordance with these systems andmethods could be formed from polyimide-amine acid salts ofstyrene-maleic anhydride copolymers containing pendant tertiary aminegroups that are neutralized to the extent of at least about 75 percentwith sufficient monocarboxylic acid having an aliphatic carbon-to-carbonchain of at least about 8 carbon atoms, preferably as a terminal group.In embodiments, a styrene-maleic anhydride copolymer can be imidized tothe extent of at least about 65 percent up to about 100 percent of itsanhydride groups, and neutralized with a dialkylaminoalkylamine to theextent of about 75 percent to 100 percent, with the long chainmonocarboxylic acid. The styrene-maleic anhydride copolymerpolyimide-amine acid salts can also contain imide groups or amide groupsup to the extent of about 35 percent of its anhydride groups by reactionwith a primary or secondary alkylamine, for instance, of about 8 to 30carbon atoms. In embodiments, the ratio of styrene to maleic anhydridein the styrene-maleic anhydride copolymer of this invention can be inthe range of about 0.1:1 to 5:1, preferably about 0.5:1 to 2:1, and mostpreferably about 1:1. In embodiments, the styrene-maleic anhydridecopolymer molecular weight can vary from about 400 to 5,000, preferablyfrom about 1,000 to 5,000, and often is in the range of about 1,400 to2,000. In embodiments, long hydrophilic chains can be attached to thecopolymer backbone.

Polymers such as those disclosed herein can be used to formulatesurfactants that have multipoint interaction with aromatic heavy oil,thus yielding utility in EOR. In embodiments, the polymers can bemodified, for example by adding hydrophilic chains (e.g., polypropyleneoxide/polyethylene oxide polymeric chains) to promote pulling emulsifiedoil drops into water.

Desalting

Desalting refers to the process of removing salts from oil, making theoil more suitable for further refining. Salts, including magnesiumchloride, sodium chloride and calcium chloride can be found in crudeoil. If allowed to remain in the crude oil during the refineryoperation, the salts can dissociate and the chloride ion can ionize toform hydrochloric acid, which, along with various organic acids found incrude oil, contributes to corrosion in refinery equipment. In addition,other metal salts (e.g., potassium, nickel, vanadium, copper, iron andzinc) can be found in the crude oil, also contributing to fouling of theequipment and end-product degradation. Crude oil also containsemulsified water, which contains dissolved salts.

Desalting crude oil takes advantage of the fact that the salts dissolvein a water phase, which is separable from the oil phase. Crude oilnaturally contains water in emulsion, as mentioned above. For certaintechniques of desalting, additional water may be added to the oil (e.g.,in an amount between 5-10% by volume of crude) so that the impuritiescan further dissolve in the water. The water-in-oil emulsion can bebroken with the assistance of emulsion-breaking chemicals and/or byexposing the emulsion to an electrical field that polarizes the waterphase, so that the water phase bearing the impurities separates from thepetroleum phase. Ethoxylated nonylphenols are a class of nonionicsurfactants that have been used for desalting crude oil according tothese principles.

The surfactant compounds and compositions disclosed herein canfacilitate the demulsification of the water-in-oil emulsion, so that theoil phase separates from the water phase, with the water phase carryingthe soluble impurities (i.e., the salts). In embodiments, thehydrophilic portion of the surfactant compound and compositions caninclude one or more ionizable carboxylic acid groups that can be ionizedat a basic pH (e.g., >8) to produce an emulsion-sustaining material asdescribed above. To destabilize the emulsion, acid may be added,removing the charge stabilization and allowing the two phases tosegregate from each other.

Sludge and Contamination Removal

In the field, the well outflow stream is first separated into its threecomponents: natural gas, crude oil and produced water. The producedwater and crude oil can form a stable emulsion that can interfere withready separation of these two components. Furthermore, water can also beintroduced into an oil-bearing formation to apply pressure to the oilwithin the formation to keep it flowing. Oil that is recovered underthese circumstances also contains a water fraction, typically dispersedas a stable emulsion. This stabilized layer of water in oil, known asthe “rag layer,” actually includes multiple phases, such as solid-in-oildispersions, water-in-oil emulsions, and oil-in-water-in-oil emulsions.

With heavy oils, there can be finely divided mineral solids or othermaterials within the production stream that can act as emulsifiers. Forexample, materials such as asphaltenes and high naphthenic acids, alongwith submicron sized solid particles such as silica, clay or otherminerals can stabilize water-in-oil emulsions where the heavy crude oilfluid comprises the continuous phase.

Asphaltenes, paraffinic waxes, resins and other high-molecular-weightcomponents of heavy crude exist in a polydisperse balance within theemulsified heavy crude fluid. A change in the temperature, pressure orchemical composition can destabilize the polydisperse crude oil. Thenthe heavy and/or polar fractions can separate from the oil mixture intosteric colloids, micelles, a separate liquid phase, and/or into a solidprecipitate. Asphaltene precipitation causes problems all along thecrude oil process. Asphaltene precipitation becomes increasinglyproblematic when crude oil is processed, transported, or stored atcooler temperatures, because the heavier components of crude oil (e.g.,asphaltenes and naphthenic acids) that remain dissolved in the heavycrude under high temperatures and pressures are no longer supported inthat state as the conditions change. When the heavy crude oil cools toambient atmospheric temperatures, these components can precipitate outof the crude oil itself and lodge at the bottom of a storage vessel ortank to form a viscous, tarry sludge. These components also becomeavailable as emulsifying agents to sustain the water-in-oil emulsionsformed as part of the rag layer. The rag layer has a higher density thanlight crude, so that it tends to sink to the bottom of storage vesselsalong with the heavy oil components and associated clay/mineral solids,contributing to the buildup of oil sludge, a thick waste material formedfrom the various deposits sedimenting out from a crude oil mixture.Sludge forms when heavier components of crude oil separate from theliquid hydrocarbon fractions by gravity and sink to the bottom of an oiltank or other containment vessel. Any given storage vessel can contain asignificant amount of sludge, which can diminish storage space foruseful crude oil and which can otherwise reduce the efficiency ofstorage tank operation. Sludge may also require removal if the storagevessel is to be maintained, repaired or inspected.

In the course of activities related to onshore production, offshoreproduction, transportation, refining, and use of oil, spills and otherundesirable releases of hydrocarbons can occur. Contaminated sedimentsare formed when oily materials contact sand, soil, rocks, beaches, andthe like. In some cases, the spills are from long term gradual releasesat industrial sites, and in other cases the spills can be fromcatastrophic accidental discharges. In either event, the contaminatedsoils will require remediation to prevent further environmental damage.The contaminated soil can be in the form of oil-soaked sediments, orwater/oil mixtures with solids, including emulsions. Since thecontaminated soils have features in common with tank bottoms sludges,the same treatment processes may be applied to both cases.

In accordance with these systems and methods, the inventive surfactantsolution and compositions comprising an amphiphilic surfactant can beused to emulsify heavy crude oil components that have settled as asludge at the bottom of the oil containment vessel. Such a surfactant orsurfactant composition can be injected into the sludge, thereby formingan oil-in-water emulsion comprising the heavy crude oil components ofthe sludge, which emulsion can then be removed from the oil containmentvessel, thereby desludging it. In embodiments, the sludge to be treatedcomprises an oil-contaminated sediment that was created by accidentaldischarge of hydrocarbons onto the ground or a body of water. Inembodiments, the sludge to be treated comprises asphaltenes, or itcomprises a water-in-oil emulsion.

In embodiments, the aqueous surfactant and/or surfactant compositionsincludes a switchable, “smart” surfactant, which can be injected as anaqueous solution into an oil storage vessel to emulsify the heavy oilsludge into the water phase with minimal agitation. Establishing wateras the continuous phase of the emulsion for the sludge can decrease thesludge viscosity so that it can be pumped out of the storage vessel intoan alternate containment system. For example, the sludge-in-wateremulsion can be directed to a distinct separation vessel, where theemulsion can then be broken, yielding a phase-separate two-componentsystem comprised of crude oil fractions suitable for further refiningand recovered water suitable for reuse in similar or other projects.

In embodiments, several steps will be required for the surfactantsystem. First, the surfactant or surfactant composition will be injectedinto the heavy oil sludge (including the rag layer), so that thesurfactant or surfactant composition can destabilize the heavy oil-waterinterface to invert the emulsion into the water phase. In this initialphase, an amphiphilic, water-soluble polymer can be used that iseffective at low concentrations. After this is accomplished, theresulting water emulsion can be removed from the subject vessel andrelocated, for example to a separation vessel. This may take place as aseparate step after the first step has been completed. In otherembodiments, however, this can take place during the first step. Forexample, the water emulsion can be siphoned off as it is formed. As afinal step, the water emulsion containing the stabilized oil dropletscan be demulsified. A change in the conditions of the water emulsion canchange the conformation of the surfactant, so that it breaks into anoil-soluble component and a water-soluble component. The oil-solublecomponent thus demulsifies the heavy oil droplets, while thewater-soluble component remains in the water phase. Surfactant moleculescan be designed so that the water-soluble byproduct is non-toxic andenvironmentally safe. The emulsification and/or separation processesmight be carried out at temperatures above ambient, to facilitate flowand emulsification or to cause switching of the surfactant properties.

Oil Shale Extraction

In embodiments, the systems and methods disclosed herein can be adaptedfor extracting hydrocarbons from the kerogen in oil shale sources. Inembodiments, theses systems and methods can mobilize kerogen to allowretorting processes to be carried out at lower temperatures than arepresently required. Processes for treating oil shales can include (A)acid etching, (B) kerogen decomposition, and (C) extraction withkerogen-based surfactants.

First, the oil shale sedimentary rock can be treated, or etched, withaqueous acid solutions. As examples, organic or inorganic acids can beused. Preferably inorganic mineral acids (hydrochloric, sulfuric,phosphoric) or waste acids are used due to lower costs. In embodiments,exposing the oil shale rock material (e.g., limestone, nahcolite, etc.)with acid for a short period of time and at relatively low temperaturescan introduce porosity, improving its permeability to fluids that willcontact it during the subsequent steps of the method. In embodiments,the acid treatment may be applied to ex-situ (i.e., mined) oil shale. Inother embodiments, the acid treatment may be applied to in-situ oilshale.

Second, the oil shale can be treated with a solution that inducesfracturing or decomposition of the kerogen molecular structure. Inembodiments, the solution can contain radical-generating chemicals andor electron transfer generators. The radical and electron transfergenerators will break carbon-carbon and ether bonds. This willfractionate the kerogen-producing fragments having lower molecularweights. In embodiments, the acid etching and kerogen decomposition aredone concurrently.

In embodiments, examples of radical/electron generators can includehydrogen peroxide, ammonium or sodium persulfate, organic peroxides suchas benzoyl peroxide, organic azo compounds such as azo-bisisobutyronitrile, zero valent iron, Fenton's reagent, and the like. Notto be bound by theory, these reagents can work by breaking bonds(carbon-carbon or ether), resulting in kerogen with lower molecularweight. The goal with this step is that in the next treatment thesurfactants will be able to emulsify at least part of the kerogen (thepart with lower molecular weight) and the other part with highermolecular weigh will have higher mobility. The mobility of the kerogenis thereby increased because the molecular weight will be lower than theoriginal condition, and also some interactions between the rock andkerogen have been destroyed by the chemical treatment.

After exposure to the radical/electron generator agents, there can be 2products. One product is an emulsion, mixture, or suspension of thelower MW kerogen fractions (degraded kerogen) in water. No retorting ofthis product is required. The degraded kerogen is extracted with anaqueous surfactant solution and subsequently separated form thesurfactant/water solution by use of switchable surfactants. Therecovered kerogen will enter the typical refining process. The secondproduct can be the residual rock containing the higher MW fractions ofkerogen. This rock will be retorted but at lower temperatures thancurrently used for oil shales. The recovered kerogen will enter thetypical refining process.

As a third step, the oil shale can be treated with surfactants designedto have high affinity for kerogen. In embodiments, the surfactants willpreferably have a hydrophilic-lipophilic balance value higher than 10 inorder to be able to form oil-in-water (O/W) emulsions, and thesurfactants can include ionic or non-ionic types. In embodiments, thestructure of the surfactant can be aliphatic and, preferably with acyclic aliphatic structure. The surfactants can preferably betemperature or pH switchable. In embodiments, the surfactant can be madefrom fractions or fragments of kerogen that have been recovered from oilshale. In embodiments, the surfactant can be made from structures thatmimic the components of kerogen. Some examples are compounds obtained bymodifying lignin by reacting some of the hydroxy groups in the ligninwith groups that provides more hydrophilic characteristics. Some ofthese groups can be carboxy terminated polyethylene oxide, succinicacids, etc.

Kerogen fragments or fractions can be isolated from oil shale byextraction or distillation, optionally in concert with thermal orchemical decomposition of the kerogen to improve mobility or solubility.The fragments or fractions, once isolated, can be modified withfunctional groups to convert them to surfactants with an affinity forkerogen. In embodiments, these modifications can include hydrophilicmodifications, such as ethoxylation, propoxylation, oxidation,sulfonation, phosphorylation, and modification with other polar groups.

In embodiments, the surfactants can be suspended in an aqueous mixture,so that they can emulsify part of the fractionated kerogens, forexample, those hydrocarbons having lower molecular weight. Inembodiments, the surfactants can increase the mobility inside the rockformation of the remaining kerogen fractions having higher molecularweights. This extraction or mobilization can be aided by the surfactantreducing the interfacial tension between the kerogen fragments and thewater phase, or by solubilizing the kerogen fragments. The extraction,chemical treatment processes can are be aided by heating the formation.An object of the invention is to reduce the total energy requirements ofrecovering kerogen.

Use of the foregoing steps can treat oil shale so that lower temperatureretorting mechanisms can be used for extracting useful hydrocarbons fromthe kerogen in the rock. These techniques can be adapted for use withsurface processing or in-situ extraction methods.

The invention is illustrated by the following examples which are notmeant to be limiting in any way.

EXAMPLES Materials

All materials were obtained from Sigma-Aldrich with the exception of EkaSA 210 that was supplied by EKA Chemicals, Inc., Marietta, Ga. 30062,USA. ERISYS GE-7: CVC Thermoset Specialties, Moorestown, N.J. 08057 USA.

Example 1 Surfactant Compositions Comprising an Aromatic Compound andAlkylated Succinic Anhydride

The composition was prepared as follows:

A 300 ml bomb is charged with resorcinol (5 g, 48 mmol) and Eka SA 210brand alkylated succinic anhydride (100% C18 chain, 16.8 g., 48 mmol).To this, acetone (150 ml) was added, the vessel is sealed and heated to80 C for 16 hours. After the reaction is complete, acetone is removedunder vacuum. The product was analyzed by IR which showed only a smallfraction of disappearance of the anhydride peak and small formation ofacid (hydrolysis of the anhydride group).

Example 2 Surfactant Compositions Comprising an Aromatic Compound andAlkylated Succinic Anhydride

The composition was prepared as follows:

A 300 ml bomb reactor was charged with resorcinol (5 g, 48 mmol) and EkaSA 210 (33.7 g, 96 mmol). To this, acetone (150 ml) was added, thevessel sealed, and heated to 80° C. for 16 hours. Then, acetone wasremoved under vacuum. The product was analyzed by IR which showed only asmall fraction of disappearance of the anhydride peak and smallformation of acid (hydrolysis of the anhydride group). NMR of theproduct indicated that attachment of the anhydride to the resorcinol wasnegligible.

Example 3 Proposed Synthesis of Compounds of Formula (II)

Compounds having the structure of formula (II) may be synthesized asfollows:

A 300 ml bomb is charged with resorcinol (5 g, 48 mmol) and glycidylhexadecyl ether (28.6 g, 96 mmol). To this, acetone (150 ml) is added,the vessel sealed, and the mixture heated to 80° C. for 16 hours. Afterthis first addition, the material is isolated and dried under vacuum.The alcohol moieties created by the epoxide ring opening is used asinitiators in an ethylene oxide polymerization to create a hydrophilicportions on the surfactant, under standard ethylene oxide polymerizationconditions. The scheme below illustrates this Synthesis III:

Example 4 Proposed Synthesis of Compounds of Formula (II)

Compounds having the structure of formula (III) may be synthesized asfollows:

A 300 ml bomb is charged with resorcinol (5 g, 48 mmol) and glycidylhexadecyl ether (14.3 g, 48 mmol). To this, acetone (150 ml) is added,the vessel sealed, and the mixture heated to 80° C. for 16 hours. Afterthis first addition, the material is isolated and dried under vacuum.The alcohol moieties created by the epoxide ring opening is used in thenext reaction to add hydrophilic portions to the molecule. Compound I isdissolved in acetone and heated to 80° C. to complete the reactionwithout the need for an ethylene oxide polymerization. The scheme belowillustrates this Synthesis IV.

Example 5 Critical Micelle Concentration

Critical micelle concentration (CMC) is an important metric withsurfactant systems. It is defined as the minimum surfactantconcentration that will form micelles. Below this amount, the moleculesexist only in a non-aggregated form. Additionally, this number alsorepresents the constant concentration of monomeric molecules insolution. Effectively, it describes a lower limit to usage and is a goodfirst approximation to formulation content.

A series of aqueous surfactant dilutions were prepared in deionizedwater with concentrations between 20 μM and 200 mM. The water surfacetension at 22° C. was measured on a KSV 702 tensiometer using the DuNouy ring method. Measured surface tensions were plotted againstconcentration and linear regression analysis was used to find theinflection point denoting the critical micelle concentration (CMC) ofthe surfactant. For testing at higher or lower pH conditions, 0.1 Mbuffer solutions were used. Citric acid buffer was used to stabilize pH3 while sodium bicarbonate was used for a pH 10 buffer.

FIG. 1 illustrates examples of critical micelle concentration of acomposition prepared according to Example 1, termed R1 in the figure.FIG. 1 also illustrates examples of critical micelle concentration of acomposition prepared according to Formula (II) formula shown below,termed R2 in the figure.

FIG. 2 shows a plot of CMC as a function of pH for two compositionsprepared according to Examples 1 and 2 (R1 and R2, respectively).

Example 6 Emulsion Stability for Oil Flow Behavior

In order to test the capabilities of the surfactants in emulsifying andtransporting heavy crude oils, the viscosity was measured with variousadditions of surfactant solution on a Brookfield viscometer at 22° C.The compositions prepared according to Examples 1 and 2, were tested.Using a LV3 type spindle at 40 RPM, the diluted bitumen (residualtoluene mixed with bitumen) demonstrated a viscosity of approximately2000 cP. This diluted bitumen was then mixed with multiple ratios of a 1wt % of the compositions in deionized water with the pH adjusted to 9for emulsion activity. FIG. 3 illustrates the results of these tests,showing the viscosity of diluted bitumen as a function of surfactantsolution addition.

FIG. 3 demonstrates that incorporation of an aqueous solution ofsurfactant can dramatically decrease the viscosity of diluted bitumen.As shown in FIG. 3, the addition of more than 50 vol % of a diluteaqueous solution of the compositions described herein decreases thebitumen viscosity by nearly one thousand times. The energy savings ofsuch a system are significant, but the concomitant increase in flowrateenables much higher throughput and residence time in a pipeline.

Example 7 Reaction Between Alkenylsuccinic Anhydride and Benzyl Alcohol

A reactor was charged with benzyl alcohol (4.821 g, 44.58 mmol) andnonenyl succinic anhydride (10 g, 44.58 mmol). The mixture was stirredfor about 2.5 hours at 130° C. under nitrogen. The product was thenanalyzed by IR spectrometry using an AVATAR 360 FT-IT spectrometer(“IR”). The sample was run in the “Attenuated Total Reflectance mode”placing the liquid sample over a Germanium crystal, which showed almostcomplete disappearance of the anhydride carbonyl peaks (1859 and 1778cm-1) (i.e., only small traces of the peaks were visible) and theappearance of the ester and acid carbonyl bands (1735 and 1700 cm-1respectively). The scheme below illustrates this synthesis:

Example 8 Reaction Between Alkenylsuccinic Anhydride and Benzyl Alcohol

A reactor was charged with benzyl alcohol (3.063 g, 28.36 mmol) and EkaSA 210 brand alkylated succinic anhydride (10 g, 28.36 mmol). Themixture was stirred for about 4 hours at 130° C. under nitrogen. Theproduct was then analyzed by IR, which showed almost completedisappearance of the anhydride carbonyl peaks (1863 and 1778 cm-1) andthe appearance of the ester and acid carbonyl bands (1735 and 1704 cm-1respectively). The scheme below illustrates this synthesis:

Example 9 Reaction Between a Phenol and an Alkenylsuccinic Anhydride

A reactor was charged with phenol (2.098 g, 22.3 mmol), noneyl succinicanhydride (5 g, 22.3 mmol), p-toluene sulfonic acid (1.92 g, 11.15 mmol)and 35 ml of toluene. The reactor was fitted with a Dean-Stark trap andthe reaction mixture was stirred for about 5 hours under reflux. Thenthe reaction was washed with water (2×25 ml) to wash the p-toluenesulfonic acid and unreacted phenol, and the solvent was stripped offunder vacuum in a rotary evaporator. The product was analyzed by IR,which showed almost complete disappearance of the anhydride carbonylpeaks (1859 and 1778 cm-1) and the appearance of a possible phenyl esterpeak at 1758 cm-1. The scheme below illustrates this synthesis:

Example 10 Reaction Between a Substituted Phenol and an AlkenylsuccinicAnhydride

A reactor was charged with 2,4-dimethylphenol (1.366 g, 11.2 mmol),noneyl succinic anhydride (2.24 g, 10 mmol), p-toluene sulfonic acid (1g, 5.8 mmol) and 35 ml of toluene. The reactor was fitted with aDean-Stark trap and the reaction mixture was stirred for about 5 hoursunder reflux. Then the reaction was washed with water (2×25 ml) to washthe p-toluene sulfonic acid and unreacted phenol and the solvent wasstripped off under vacuum in a rotary evaporator. The product was thenanalyzed by IR, which showed almost complete disappearance of theanhydride carbonyl peaks (1859 and 1778 cm-1) and the appearance of apossible phenyl ester peak at 1754 cm-1. The scheme below illustratesthis synthesis:

Example 11 Reaction Between an Alkenylsuccinic Anhydride and BenzylAmine

A reactor was charged with benzyl amine (2.388 g, 22.3 mmol), noneylsuccinic anhydride (5 g, 22.3 mmol) and 15 ml of THF. The mixture wasstirred for about 1 hour at room temperature, and then the solvent wasstripped off under vacuum in a rotary evaporator. The product was thenanalyzed by IR, which showed almost complete disappearance of theanhydride carbonyl peaks (1859 and 1778 cm-1) and the appearance of theamide and acid carbonyl bands (1645 and 1548 for amide I and IIrespectively, and 1723 cm-1 for associated acid). The scheme belowillustrates this synthesis:

Example 12 Reaction Between an Alkenylsuccinic Anhydride and M-PhenyleneDiamine

A reactor was charged with m-phenylene diamine (1.534 g, 14.2 mmol), EkaSA 210 brand alkylated succinic anhydride (10 g, 28.4 mmol) and 20 ml ofTHF. The mixture was stirred for about 1.5 hours at RT. Then the solventwas stripped off under vacuum in a rotary evaporator. The product wasthen analyzed by IR, which showed almost complete disappearance of theanhydride carbonyl peaks (1863 and 1782 cm-1) and the appearance of theamide and acid carbonyl bands (1548 for amide II and a broad peak withmaximum at 1703 cm-1). The appearance of these peaks may be explained byan overlapping of the amide I and acid peaks. The scheme belowillustrates this synthesis:

Example 13 Interfacial Tension (IFT) Measurements of Surfactants

Solutions of different aromatic based surfactants, described in Table 1below, were dissolved in aqueous solution at 1% by weight. Deionizedwater was used as the control. Each aromatic-based surfactant wasformulated in accordance with the corresponding Example as listed inTable 1. The pH of each solution was adjusted to 9 by the addition of 1M sodium hydroxide. Using a KSV Sigma 702 tensiometer, the interfacialtension was measured for each solution at the interface with air,toluene and Exxon ISOPAR M fluid. Values are reported in Table 1.

TABLE 1 Table 1: Interfacial tension measurements for 1% surfactantsolutions at the interface of air, toluene and ISOPAR IFT w/ IFT w/ IFTw/air Toluene ISOPAR Compound Example [mN/m] [mN/m] [mN/m] 1 DeionizedWater Control 71.88 33.12 72.38 2 Heated mixture of 2 26.36 <0.01 <0.01m-resorcinol and octadecen-1-yl succinic anhydride 3 2-(octadecen-1- 828.14 3.73 8.76 yl)succinic acid monobenzyl ester 4 2-(nonen-1- 7 32.933.13 3.03 yl)succinic acid monobenzyl ester

Example 14 Interfacial Tension (IFT) Measurements of Surfactants

The interfacial tension with air was measured for decreasing aqueousconcentrations of a surfactant composition prepared in accordance withExample 2, starting at 1.0% by weight, 0.50% by weight and 0.10% byweight. Additionally, an unheated blend of m-resorcinol andoctadecen-1-yl succinic anhydride was dissolved at the sameconcentrations for each compound as was used in Example 1 forcomparison. Two commercially available surfactants were also tested:Tergitol 15-S-7 and Igepal CO-890. Table 2 presents the results of theIFT measurements with air for each of the tested compounds at the threedifferent concentrations.

TABLE 2 Solution (by weight) 0.10% 1.00% 0.50% IFT IFT w/air IFT w/airw/air Surfactant Name [mN/m] [mN/m] [mN/m] Heated mixture ofm-resorcinol and 26.36 27.07 27.92 octadecen-1-yl succinic anhydrideUnheated mixture of m-resorcinol and 26.45 27.76 29.16 octadecen-1-ylsuccinic anhydride Tergitol 15-S-7 28.03 28.22 28.11 Igepal CO-890 44.6644.63 44.38

Example 15 Surfactant Properties

A sample of a compound prepared in accordance with Example 7 wasdissolved in aqueous solution at 1% by weight and the pH of the solutionwas adjusted to 9 by addition of 1 molar sodium hydroxide. 2 mL of heavyoil (API gravity index=15.0 degrees) was mixed at 50:50 volume ratiowith the surfactant solution. The mixture was shaken lightly and left tosit for 1 hour to determine the time stability of the emulsion. Afterabout 1 hour, approximately 0.5 mL of water had phase separated in thebottom of the vial. The same phase separation was observed after 2 daysof leaving the sample at rest. A magnified image of the oil dropletsformed in emulsion is presented in FIG. 4, showing emulsion of heavy oil(API 15) at 50× magnification using the surfactant of Example 7. Duringobservation, some coalescence of droplets was observed, however, thestability of the emulsion was evident over multiple days.

Example 16 Surfactant Properties

A 1% by weight sample of the compound prepared in accordance withExample 7 was prepared in aqueous solution and pH adjusted to 9 by theaddition of 1 M sodium hydroxide, to form a surfactant solution. Heavyoil (API gravity index 15.0) was combined with the surfactant solutionat varying water ratios to form the emulsion. Each sample was thentested in a Brookfield DVIII+Rheometer for viscosity. FIG. 5 depicts theviscosity of the resulting emulsion for a given water ratio. With use ofthe surfactant, a large drop in viscosity of the heavy oil is observed,even for lower water ratios. An additional drop in viscosity was notedwhen the volume % of water exceeded 50%.

Example 17 Reaction Between a Phenylene Diamine and Hydrophobic andHydrophilic Glycidyl Ether

A reactor was charged with m-phenylene diamine (2 g, 18.5 mmol), ERISYSGE-7 brand monoglycidyl ether of a naturally occurring C8-C10 aliphaticalcohol (3.44 g, 18.5 mmol), and 15 ml of THF. The mixture was stirredfor 2 hours under reflux. Then a solution of polyethylene glycoldiglycidyl ether (9.731 g, 18.5 mmol) in 10 ml of THF was added and thereflux continued for additional 4 hours. Then the solvent was strippedoff under vacuum. The product was tested qualitatively to assess certainproperties. First, the product was dissolved in water to show that it iswater-soluble. Second, the water solution of the product was agitatedvigorously, and a foam was formed, suggesting its hydrophilic andhydrophobic nature. It is envisioned that the product of this reactionwill have an aromatic ring in the middle and 2 polymeric “legs”depending from it, a hydrophilic (polyethylene glycol) and a hydrophobic(alkyl chain) chain. The scheme below illustrates this synthesis:

Example 18 Oily Sand Treatment

30 grams of washed sand (50/70 mesh) was mixed with 3 grams of lightcrude oil (API gravity index=28) by stirring until the oil was evenlydistributed over the surface of the sand. For this experiment, thesurfactant composition prepared in accordance with Example 2 (SurfactantA) was tested. 150 mL of a 1% surfactant solution (Surfactant A) wasmixed with the oily sand by sealing in a jar and shaking by hand at amoderate pace for 5 minutes. The contents of the jar were left to sitfor 1 hour and then the liquid layer was decanted from the sand. The jarwas placed in an oven under vacuum at 100° C. for 3 hours, then cooledto room temperature. A sample of the dried sand was weighed and placedin a muffle furnace at 650° C. for 3 hours, then reweighed to determinethe total remaining weight of hydrocarbon on the sand surface. Table 3summarizes the effect of the surfactant solutions.

TABLE 3 Solution used to wash % Oil remaining in oily- % Oil Recovery byoily-sand sand after wash Solution None 8.83% Deionized water 7.90%10.54% 1% Surfactant A 0.86% 90.24%

EQUIVALENTS

While specific embodiments of the subject invention have been discussed,the above specification is illustrative and not restrictive. Manyvariations of the invention will become apparent to those skilled in theart upon review of this specification. Unless otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asbeing modified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth herein areapproximations that can vary depending upon the desired propertiessought to be obtained by the present invention.

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

1. A composition comprising an aromatic compound and a substitutedsuccinic anhydride, wherein the aromatic compound has the Formula VIII:Ar-[G₄]_(p); and the substituted succinic anhydride has the Formula IX:

wherein Ar is selected from the group consisting of aryl, arylalkyl andheteroaryl, each optionally substituted; each G₄ is independentlyselected from the group consisting of OR₂, SR₂, N(R₂)₂, COOR₂, OCOR₂,COR₂, CON(R₂)₂ and N(R₂)₂CO; each R₂ is independently selected from thegroup consisting of H and lower alkyl; R₈ is a saturated or unsaturatedhydrophobic aliphatic group; and p is 1 or
 2. 2. The composition ofclaim 1, wherein p is
 2. 3. The composition of claim 1, wherein thehydrophobic aliphatic group is selected from the group consisting alkyl,alkenyl, alkadienyl, alkynyl, cycloalkyl, cycloalkenyl, aryl andheteroaryl.
 4. The composition of claim 3, wherein the hydrophobicaliphatic group is selected from the group consisting of alkyl, alkenyl,and alkadienyl.
 5. The composition of claim 4, wherein the hydrophobicaliphatic group is selected from the group consisting of C8-C20 alkyl,C8-C20 alkenyl and C8-C20 alkadienyl.
 6. The composition of claim 2,wherein Ar is optionally substituted phenyl or optionally substitutedbenzyl.
 7. The composition of claim 6, wherein G₄ is selected from theOR₂ or N(R₂)₂.
 8. The composition of claim 7, wherein G₄ is OR₂, whereinR₂ is H.
 9. The composition of claim 8, wherein p is
 2. 10. Thecomposition of claim 9, wherein the aromatic compound is resorcinol. 11.The composition of claim 10, wherein the R₈ is selected from the groupconsisting of C8-C20 alkyl, C8-C20 alkenyl and C8-C20 alkadienyl.
 12. Acomposition comprising an aromatic compound and a substituted succinicanhydride, wherein the aromatic compound is resorcinol; and thesubstituted succinic anhydride has the Formula IX

wherein R₈ is a saturated or unsaturated hydrophobic aliphatic group.13. The composition of claim 12, wherein the aromatic compound ism-resorcinol.
 14. A composition comprising an aromatic compound and acompound of Formula X wherein the aromatic compound has the FormulaVIII:Ar-[G₄]_(p); and the compound of Formula X is:

wherein Ar is selected from the group consisting of aryl, arylalkyl orheteroaryl; each G₄ is independently selected from the group consistingof OR₂, SR₂, N(R₂)₂, COOR₂, OCOR₂, COR₂, CON(R₂)₂ and N(R₂)₂CO; each R₂is independently selected from the group consisting of H and loweralkyl; R₈ is a saturated or unsaturated hydrophobic aliphatic group; andp is 1 or
 2. 15. The composition of claim 14, further comprising analkylene oxide.
 16. The composition of claim 15, wherein the alkyleneoxide is ethylene oxide or propylene oxide.
 17. The composition of claim14, wherein R₂ a lower alkyl.
 18. The composition of claim 14, whereinAr is phenyl or benzyl.
 19. The composition of claim 18, wherein G₄ isselected from the OR₂ or N(R₂)₂.
 20. The composition of claim 19,wherein G₄ is OR₂, wherein R₂ is H.
 21. The composition of claim 20,wherein p is
 2. 22. A method for extracting oil from an oil mixturecomprising: (a) adding a composition of claim 1 to an oil mixture, and(b) collecting the oil.
 23. The method of claim 22, wherein the oilmixture comprises oil sands, wherein said method further comprisesadding water to the mixture.
 24. The method of claim 22, wherein the oilmixture is a waterborne oil slick.
 25. The method of claim 22, whereinthe oil mixture formed by step (a) is transported via a pipeline. 26.The method of claim 22, wherein step (a) occurs in an oil well toenhance oil recovery.
 27. A method of removing water and associatedsalts from oil, comprising: (a) contacting the oil with a composition ofclaim 1, and (b) separating the water from the oil.
 28. A compoundhaving the formula XI:

wherein Ar₂ is a substituted or unsubstituted phenyl or benzyl; p is 1or 2; m is 1 or 2; n is 0 or 1; each G₁ is independently selected fromthe group consisting of OC(O), C(O)O, C(O), C(O)NR₂ and NR₂CO; G₂ isabsent; each R₂ is independently H or a lower alkyl; G₃ is independentlyabsent, or (CH₂)_(q); q is 1, 2, 3, 4 or 5; R is a hydrophilic group;and R₁ is a saturated or unsaturated hydrophobic aliphatic group. 29.The compound of claim 28, wherein Ar is substituted or unsubstitutedbenzyl.
 30. The compound of claim 28, wherein Ar is substituted orunsubstituted phenyl.
 31. The compound of claim 28, wherein the R isCOOH.
 32. The compound of claim 28, wherein R₁ is a C8-C20 alkyl, C8-C20alkenyl or C8-C20 alkadienyl.
 33. The compound of claim 28, wherein G₁is OC(O) or NHC(O).
 34. The compound of claim 29, having the formulaXII:

wherein t is 0 or 1; G₅ is O or NH; and R₁ is a saturated or unsaturatedhydrophobic aliphatic group.
 35. The compound of claim 34, wherein R₁ isa C8-C20 alkyl, C8-C20 alkenyl or C8-C20 alkadienyl.
 36. The compound ofclaim 28, having the Formula XIII:

wherein each t is independently 0 or 1; and R₁ is a saturated orunsaturated hydrophilic aliphatic group.
 37. A compound having theFormula XIV:L-G₅-Ar-G₅-M; wherein Ar is aryl, arylalkyl and heteroaryl, eachoptionally substituted; Each G₅ is independently G₅ is O or NH; L is ahydrophilic polyethylene glycol glycidyl ether; and M is a hydrophobicglycidylalkyl ether.
 38. The compound of claim 37, wherein Ar is phenyl.39. A method for extracting oil from an oil mixture comprising: (a)adding a compound of claim 28 to an oil mixture, and (b) collecting theoil.
 40. The method of claim 39, wherein the oil mixture comprises oilsands, wherein said method further comprises adding water to themixture.
 41. The method of claim 39, wherein the oil mixture is awaterborne oil slick.
 42. The method of claim 39, wherein the oilmixture formed by step (a) is transported via a pipeline.
 43. The methodof claim 39, wherein step (a) occurs in an oil well to enhance oilrecovery.
 44. A method of removing water and associated salts from oil,comprising: (a) contacting the oil with a compound of claim 28 and (b)separating the water from the oil.
 45. A surfactant compositioncomprising the compound of claim
 28. 46. The surfactant composition ofclaim 45, wherein the composition is at a basic pH.
 47. The surfactantcomposition of claim 46, wherein the pH of the composition is at leastabout
 8. 48. The surfactant composition of claim 47, wherein the pH ofthe composition is between about 8 and
 9. 49. The method of claim 44,wherein the compound is in a composition which has a basic pH.